Naphthalene dicarboxylic acids are monomers that are known to be useful for the preparation of a variety of polymers. For example, poly(ethylene 2,6-naphthalate) prepared from 2,6-naphthalene dicarboxylic acid and ethylene glycol has better heat resistance and mechanical properties than polyethylene terephthalate and is useful in the manufacture of films and fibers.
Dimethylnaphthalenes are desirable feedstocks for oxidation to the corresponding naphthalene dicarboxylic acids. A known conventional process for producing a naphthalene dicarboxylic acid comprises the oxidation of a dimethylnaphthalene with oxygen in the liquid phase in an acetic acid solvent at an elevated temperature and pressure and in the presence of a catalyst comprising cobalt, manganese and bromine components.
Typically, dimethylnaphthalenes are found in refinery or coal-derived streams as mixtures of all of the ten possible dimethylnaphthalene isomers. However, separation of these isomers is very difficult and expensive. Consequently, methods for producing specific dimethylnaphthalenes or mixtures of two or three specific dimethylnaphthalenes in high purity and quality are highly desirable. One such method is a multistep synthesis involving: (1) the formation of an alkenylbenzene by the reaction of o-, m- or p-xylene or ethylbenzene with butadiene; (2) the cyclization of the resulting alkenylbenzene to form one or more dimethyltetralins belonging to one or two of three groups of isomeric dimethyltetralins--that is, either the group containing the 1,5-, 1,6-, 2,5- and 2,6-dimethyltetralins, the group containing the 1,7-, 1,8- 2,7- and 2,8-dimethyltetralins, or the group containing the 1,3-, 1,4-, 2,3- 5,7- 5,8- and 6,7-dimethyltetralins; (3) the dehydrogenation of the dimethyltetralin(s) to form the corresponding dimethylnaphthalene(s), and (4) the isomerization of the resulting dimethylnaphthalene(s) to the desired specific dimethylnaphthalene. The 1,5-, 1,6-, and 2,6-dimethylnaphthalenes make up the group that is commonly referred to as the Group A triad. The 1,7-, 1,8- and 2,7-dimethylnaphthalenes make up the group that is commonly referred to as the Group B triad. The 1,3-, 1,4- and 2,3-dimethylnaphthalenes make up the group that is commonly referred to as the Group C triad. In this regard, it is known that in the presence of an acid catalyst, the dimethylnaphthalene isomers are isomerizable within each triad of dimethylnaphthalene isomers--that is, within the 1,5- 1,6- and 2,6-dimethylnaphthalenes of triad A, within the 1,7- 1,8-, and 2,7-dimethylnaphthalenes of triad B, and within the 1,3-, 1,4- and 2,3-dimethylnaphthalenes of triad C. It is also known that the interconversion of a dimethylnaphthalene isomer within one of the aforesaid triads to a dimethylnaphthalene isomer within another of the aforesaid triads occurs to a relatively lesser extent.
For example, Sikkenga et al., U.S. Pat. No. 4,950,825 discloses an improved method for preparing one or more dimethyltetralins from 5-(o-, m-, or p-tolyl)-pent-1- or -2-ene or 5-phenyl-hex-1- or -2-ene as the first feedstock which comprises contacting the first feedstock in liquid form with a solid cyclization catalyst comprising an acidic, ultrastable crystalline aluminosilicate molecular sieve Y-zeolite that is substantially free of adsorbed water, and at a temperature in the range of from about 120.degree. C. to about 350.degree. C. and at a pressure that is sufficiently high to maintain the first feedstock substantially in the liquid phase to thereby cyclize the first feedstock to form a first liquid product comprising one or more dimethyltetralins, wherein water is at a concentration in the first feedstock of from 0.0 up to less than about 0.5 weight percent, based on the weight of the feedstock, wherein (a) when the first feedstock comprises 5-(o-tolyl)-pent-1- or -2-ene, at least 80 weight percent of the dimethyltetralin product formed is comprised of 1,5-, 1,6-, 2,5- or 2,6-dimethyltetralin or a mixture thereof, (b) when the first feedstock comprises 5-(m-tolyl)-pent-1- or -2-ene, at least 80 weight percent of the mixture of the dimethyltetralin product formed is comprised of 1,5- 1,6- 1,7-1,8- 2,5-, 2,6-, 2,7- or 2,8-dimethyltetralin or a mixture thereof, (c) when the first feedstock comprises 5-(p-tolyl)-pent-1- or -2-ene, at least 80 weight percent of the dimethyltetralin product formed is comprised of 1,7-, 1,8-, 2,7- or 2,8-dimethyltetralin or a mixture thereof, and (d) when the first feedstock comprises 5-phenyl-1- or -2-hexene, at least 80 weight percent of the dimethyltetralin product formed is comprised of 1,3-, 1,4-, 2,3-, 5,7-, 5,8- or 6,7-dimethyltetralin or a mixture thereof.
Thompson, U.S. Pat. Nos. 3,775,496; 3,775,497; 3,775,498; and 3,775,500 disclose processes for the cyclization of specific alkenylbenzenes to one or more specific dimethyltetralins at 200.degree.-450.degree. C. in the presence of any suitable solid acidic cyclization catalyst such as acidic crystalline zeolites as well as silica-alumina, silica-magnesia, and silica-alumina-zirconia and phosphoric acid, followed by the dehydrogenation of the resulting dimethyltetralin(s) in the vapor state to the corresponding dimethylnaphthalene(s) in a hydrogen atmosphere at 300.degree.-500.degree. C. and in the presence of a solid dehydrogenation catalyst such as noble metals on carriers and chromia-alumina, and thereafter isomerization of each of the aforesaid dimethylnaphthalene(s) to the desired isomer within the triad of dimethylnaphthalenes to which the isomer being isomerized belongs at 275.degree.-500.degree. C. in the presence of a solid acidic isomerization catalyst of the same type as described in respect of the cyclization disclosed therein. In the alternative, both the cyclization and isomerization reactions can be performed in the liquid phase, in which case the cyclization is performed at 200.degree.-275.degree. C. with a solid phosphoric acid catalyst, at 70.degree.-140.degree. C. with an acidic ion exchange resin, an acidic crystalline zeolite, hydrofluoric or sulfuric acid as the catalyst or a siliceous cracking catalyst.
More specifically, Thompson, U.S. Pat. No. 3,775,496, discloses the cyclization of 5-(m-tolyl)-pent-2-ene to 1,6- and 1,8-dimethyltetralins, which are then dehydrogenated to 1,6- and 1,8-dimethylnaphthalenes, which in turn are isomerized to 2,6- and 2,7-dimethylnaphthalenes, respectively. Thompson, U.S. Pat. No. 3,775,497, discloses the cyclization of 5-phenyl-hex-2-ene to 1,4-dimethyltetralin which is then dehydrogenated to 1,4-dimethylnaphthalene, which is in turn isomerized to 2,3-dimethylnaphthalene. Thompson, U.S. Pat. No. 3,775,498, discloses the cyclization of 5-(o-tolyl)pent-2-ene to 1,5-dimethyltetralin, which is then dehydrogenated to 1,5-dimethylnaphthalene, which is in turn isomerized to 2,6-dimethylnaphthalene. Thompson, U.S. Pat. No. 3,775,500 discloses the cyclization of 5-(p-tolyl)pent-2-ene to 1,7-dimethyltetralin, which is then dehydrogenated to 1,7-dimethylnaphthalene, which in turn is isomerized to 2,7-dimethylnaphthalene.
A problem in such prior art methods is the presence of impurities such as unconverted alkenylbenzene as well as by-products, particularly heavy, high-boiling by-products, in the cyclization reaction product. Additionally, because the cyclization reaction is exothermic, prior art processes that utilize a fixed bed of cyclization catalyst are undesirable. The fixed bed reactors can develop hot spots in the catalyst bed because the heat from the reaction cannot be rapidly dissipated. Such hot spots cause catalyst deactivation and increased formation of reaction by-products.
Consequently, it is highly desired to provide for an improved cyclization step in the aforesaid synthesis of dimethyltetralin isomers, which upon dehydrogenation are subsequently converted to dimethylnaphthalene.